CN104871359A - Sulfide-solid-electrolyte manufacturing method - Google Patents

Sulfide-solid-electrolyte manufacturing method Download PDF

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Publication number
CN104871359A
CN104871359A CN201380064390.2A CN201380064390A CN104871359A CN 104871359 A CN104871359 A CN 104871359A CN 201380064390 A CN201380064390 A CN 201380064390A CN 104871359 A CN104871359 A CN 104871359A
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container
solid electrolyte
electrolyte
sulfide
temperature
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CN104871359B (en
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柳拓男
田中拓海
橘内真一郎
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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Abstract

The primary purpose of the present invention is to provide a sulfide-solid-electrolyte manufacturing method whereby a sulfide solid electrolyte that makes it easy to improve ion conduction performance can be manufactured. The present invention is a sulfide-solid-electrolyte manufacturing method that includes the following steps: a loading step in which a feedstock for manufacturing a sulfide solid electrolyte consisting primarily of a substance that can be represented by the general formula (100-x)(0.75Li2S-0.25P2S5)-xLiI (with 0 < x < 100) is loaded into a vessel; and an amorphization step, after the loading step, in which the feedstock is amorphized. The temperature of the reaction site inside the vessel during the amorphization step is controlled such that the variable x in the above general formula and the temperature (y, in DEG C) of the reaction site inside the vessel satisfy the relation y < -2.00x + 1.79102.

Description

The manufacture method of sulfide solid electrolyte
Technical field
The present invention relates to the manufacture method of sulfide solid electrolyte, especially, relate to the manufacture method of the sulfide solid electrolyte using the raw material comprising LiI to manufacture.
Background technology
Lithium rechargeable battery is high with secondary cell phase specific energy density in the past, can carry out work with high voltage.Therefore, use in the information equipments such as mobile phone as the secondary cell being easy to realize miniaturization and, in recent years, as the demand of the large-sized power purposes such as used for electric vehicle or Hybrid Vehicle also just surging.
The dielectric substrate that lithium rechargeable battery has anode layer and negative electrode layer and is configured between them, as the electrolyte for dielectric substrate, the material etc. of liquid, the solid shape of such as known non-water system.When using liquid electrolyte (hereinafter referred to as " electrolyte "), electrolyte is easy to the internal penetration to anode layer, negative electrode layer.Therefore, be easy to the interface forming anode layer or the active material contained by negative electrode layer and electrolyte, be easy to performance is improved.But widely used electrolyte is flammable, therefore need to carry the system for guaranteeing fail safe.On the other hand, when using electrolyte (hereinafter referred to as " solid electrolyte ") of the solid shape of anti-flammability, then said system can be simplified.Therefore, the exploitation possessing the lithium rechargeable battery (hereinafter sometimes referred to as " all-solid-state battery ") of the form of the layer (hereinafter referred to as " solid electrolyte layer ") containing solid electrolyte is carried out.
As the technology relevant with spendable solid electrolyte in such all-solid-state battery, such as, in patent documentation 1, disclose and utilize mechanical milling method to manufacture Li 2s-P 2s 5it is the technology of crystallized glass (lithium ion conducting sulfide based crystallized glass).
Prior art document
Patent documentation
Patent documentation 1: JP 2005-228570 publication
Summary of the invention
Invent problem to be solved
As the Li of sulfide solid electrolyte with ionic conductivity 2s-P 2s 5be the Li that with the addition of LiI in electrolyte 2s-P 2s 5-LiI electrolyte, can manifest high ionic conduction performance.This Li 2s-P 2s 5-LiI electrolyte can use the mechanical milling method disclosed in patent documentation 1 to manufacture.But, manufacturing Li by the technology disclosed in patent documentation 1 2s-P 2s 5in the electrolytical situation of-LiI, there is the Li being easy to manufacture the reduction of ionic conduction performance 2s-P 2s 5the electrolytical problem of-LiI.
Therefore, problem of the present invention is to provide the manufacture method that the raw material manufacture comprising LiI can be used to improve the sulfide solid electrolyte of the sulfide solid electrolyte of ionic conduction performance.
For solving the means of problem
The present inventor, through found that of studying with keen determination, will use the raw material manufacture comprising LiI with general formula (100-x) (0.75Li 2s0.25P 2s 5) sulfide solid electrolyte of xLiI (x is 0 < x < 100) for main body time synthesizing sulfide glass container in reacting field temperature when being set to y [DEG C], if y reaches more than set point of temperature, then specific crystalline phase (Li 3pS 4-LiI crystalline phase, Li 3pS 4crystalline phase.Identical below.) occur, the ionic conduction performance with the sulfide solid electrolyte of this specific crystalline phase is easy to reduce.Further, the present inventor finds, reacting field temperature y in container when controlling synthesizing sulfide glass by the mode meeting defined terms formula with above-mentioned x and y, the appearance of above-mentioned specific crystalline phase can be prevented, its result, can manufacture the sulfide solid electrolyte that improve ionic conduction performance.And, the present inventor finds, reacting field temperature y in container when controlling synthesizing sulfide glass by the mode meeting defined terms formula with above-mentioned x and y, prevent the appearance of above-mentioned specific crystalline phase on the one hand, be easy to the productivity ratio improving the sulfide solid electrolyte that ionic conduction performance is improved on the one hand.The present invention finds based on these and completes.
In order to solve above-mentioned problem, present invention employs following means.That is,
The present invention is the manufacture method of sulfide solid electrolyte, and it has: drop into operation: will for the manufacture of with general formula (100-x) (0.75Li 2s0.25P 2s 5) (wherein x is 0<x<100 to xLiI.Identical below.) for the sulfide solid electrolyte of main body raw material drop into container; With decrystallized operation: after this input operation, above-mentioned raw materials is decrystallized; Wherein, the mode meeting following formula (1) with the reacting field temperature y [DEG C] in the container in the x comprised in above-mentioned general formula and decrystallized operation controls the reacting field temperature in said vesse,
Y <-2.00x+1.79 × 10 2formula (1)
At this, in the present invention, " with general formula (100-x) (0.75Li 2s0.25P 2s 5) the xLiI sulfide solid electrolyte that is main body " and refer to that sulfide solid electrolyte comprises by general formula (100-x) (0.75Li 2s0.25P 2s 5) ratio of sulfide solid electrolyte that represents of xLiI is at least more than 50mol%.In addition, " for the manufacture of with general formula (100-x) (0.75Li 2s0.25P 2s 5) xLiI is the raw material of the sulfide solid electrolyte of main body " as long as can Li be manufactured 2s-P 2s 5the electrolytical raw material of-LiI (below sometimes simply referred to as " electrolyte raw material ") just without particular limitation of.As such electrolyte raw material, except Li 2s, P 2s 5and outside the combination of LiI, also can illustrate the combination etc. of other raw material comprising Li, P, S and I.In addition, in the present invention, " input operation ", as long as at least drop into the operation of electrolyte raw material in container, also can be the operation dropping into the liquid used in the mechanical milling method of such as wet type drop into electrolyte raw material in container while.In addition, in the present invention, " decrystallized operation " can be the mechanical milling method of the wet type of the liquid using hydrocarbon etc. not react with the electrolyte of raw material, generation, and can be the mechanical milling method of the dry type not using this liquid, also can be melting and sharp cooling.In addition, also can use by the heating raw materials dropped in container, stir to make it reaction and by the method beyond decrystallized for raw material mechanical lapping.Be explained, when carrying out the decrystallized operation of decrystallized mode by mechanical milling method, " mode of (1) controls the reacting field temperature in container to satisfy equation " means that the mode meeting formula (1) with the maximum temperature of the reacting field in decrystallized operation controls the reacting field temperature in container.On the other hand, when carrying out the decrystallized operation of decrystallized mode by melting and sharp cooling, " mode of (1) controls the reacting field temperature in container to satisfy equation " means with in decrystallized operation, becomes y>=-2.00x+1.79 × 10 once be warmed up to 2temperature after chilling time arrival temperature (minimum temperature) mode that meets formula (1) control in container reacting field temperature.
Controlling by having the mode meeting above-mentioned formula (1) with the reacting field temperature y in container when raw material is decrystallized, simultaneously by decrystallized for raw material decrystallized operation, can not make to become specific crystallization that ionic conductivity reduces reason and producing and manufacture Li 2s-P 2s 5-LiI electrolyte.By not making to become the crystallization generation that ionic conductivity reduces reason, becoming and being easy to improve the Li manufactured 2s-P 2s 5the electrolytical ionic conduction performance of-LiI.
In addition, in the invention described above, x can be x >=20 (20≤x < 100).
In addition, in the invention described above, in decrystallized operation, the reacting field temperature in container is preferably made to be more than 40 DEG C.In this way, be easy to improve speed that is raw material is decrystallized, synthesizing sulfide glass, therefore become the manufacturing cost easily reducing sulfide solid electrolyte.
In addition, in the invention described above, further, the mode preferably meeting following formula (2) with x and reacting field temperature y controls the reacting field temperature in container.In this way, prevent the appearance of above-mentioned specific crystalline phase, be easy to the speed improving synthesizing sulfide glass simultaneously, therefore become the productivity ratio being easy to improve the sulfide solid electrolyte that ionic conduction performance is improved.
Y >-2.00x+1.52 × 10 2formula (2)
In addition, in the invention described above, in decrystallized operation, preferably in container, give heat energy.In this way, by controlling the heat energy given, the aggregate velocity easily controlling chalcogenide glass is become.Its result, improves the aggregate velocity of chalcogenide glass, and becomes the sulfide solid electrolyte easily manufacturing and have excellent ionic conduction performance.
At this, " in container, give heat energy ", except being heated except giving the mode of heat energy in container by the outside from container, external heat source is not used can in container, to make heat energy produce yet even if can exemplify, and by suppress heat release make the reacting field temperature in container be the mode of more than set point of temperature (such as, in mechanical milling method, use the mode of container larger compared with the container that uses when heating with the outside from container) etc.
In addition, in the invention described above, decrystallized operation can be by decrystallized for raw material operation by the mechanical milling method of wet type.Even this mode, the sulfide solid electrolyte that the raw material manufacture ionic conduction performance comprising LiI is improved also can be used.
Invention effect
According to the present invention, can provide and the raw material that comprises LiI can be used to the manufacture method of the sulfide solid electrolyte of the sulfide solid electrolyte manufacturing ionic conduction performance and be improved.
Accompanying drawing explanation
Fig. 1 is the figure of the manufacture method that sulfide solid electrolyte of the present invention is described.
Fig. 2 is the figure of illustrative experiment result.
Fig. 3 is the figure representing X-ray diffraction measurement result.
Fig. 4 is the figure representing X-ray diffraction measurement result.
Embodiment
Below, with reference to accompanying drawing, the present invention will be described on one side.Be explained, the mode below illustrated is illustration of the present invention, the invention is not restricted to the following mode illustrated.
Fig. 1 is the figure of the manufacture method (hereinafter sometimes referred to as " manufacture method of the present invention ") that sulfide solid electrolyte of the present invention is described.Manufacture method of the present invention shown in Fig. 1 has input operation (S1), decrystallized operation (S2), recovery process (S3) and drying process (S4).
Drop into operation (hereinafter sometimes referred to as " S1 ") to drop into for the manufacture of Li in container 2s-P 2s 5the operation of the electrolytical raw material of-LiI.Such as, at the mechanical milling method synthesis Li that decrystallized operation described later is by wet type 2s-P 2s 5when the electrolytical operation of-LiI, S1 can be set to drop in container electrolyte raw material and not with the Li of this electrolyte raw material, synthesis 2s-P 2s 5the operation of the liquid of the hydrocarbon of-LiI electrolyte reaction etc.
At this, as electrolyte raw material spendable in S1, Li can be illustrated 2s, P 2s 5with the combination of LiI, the combination etc. comprising other raw material of Li, P, S and I.In addition, as liquid spendable in S1, the alkane such as heptane, hexane, octane can be illustrated, the aromatic hydrocarbons etc. such as benzene,toluene,xylene.
Decrystallized operation (hereinafter sometimes referred to as " S2 ") be by decrystallized for the raw material that drops in container in S1 come the operation of synthesizing sulfide glass.In S1, when dropping into electrolyte raw material and liquid in container simultaneously, S2 can be set to by the mechanical milling method of wet type by decrystallized for raw material come the operation of synthesizing sulfide glass.On the other hand, in S1, when asynchronously dropping into liquid when dropping into electrolyte raw material in container, S2 can be set to by the mechanical milling method of dry type by decrystallized for raw material come the operation of synthesizing sulfide glass.In addition, S2 also can be set to by melting and sharp cooling by decrystallized for raw material come the operation of synthesizing sulfide glass.But, from the viewpoint of become by can process at normal temperatures easily to reduce the mode etc. of manufacturing cost, S2 is preferably set to the operation by mechanical lapping (wet type or dry type) method synthesizing sulfide glass.Further, preventing feedstock composition from adhering on the wall of container etc. from the viewpoint of becoming, easily obtaining the mode etc. of the higher chalcogenide glass of amorphism, be more preferably the operation of the mechanical milling method synthesizing sulfide glass by wet type.Be explained, to exist reaction atmosphere, reaction vessel with melting and sharp cooling and limit relative, mechanical milling method has the advantage of the chalcogenide glass that can synthesize target composition easily.
In order to not form the Li reduced by ionic conduction performance 2s-P 2s 5-LiI electrolyte and the specific crystalline phase confirmed, in S2, with by general formula (100-x) (0.75Li 2s0.25P 2s 5) xLiI represents Li 2s-P 2s 5the mode that LiI content x [mol%] (the content x [mol%] of the LiI contained in electrolyte raw material) during-LiI electrolyte and the reacting field temperature y [DEG C] in the container in decrystallized operation during synthesizing sulfide glass meets following formula (1) controls the reacting field temperature y in container, synthesizing sulfide glass.
Y <-2.00x+1.79 × 10 2formula (1)
Like this, controlled the reacting field temperature in container by the mode meeting above-mentioned formula (1) with x and y, synthesizing sulfide glass, can prevent the Li reduced by ionic conduction performance on one side 2s-P 2s 5-LiI electrolyte and the formation of the specific crystalline phase confirmed.Its result, can manufacture the sulfide solid electrolyte (Li that ionic conduction performance is improved 2s-P 2s 5-LiI electrolyte.Identical below.)。
Be explained, the present inventor finds, in the outside heating not from the container of regulation, when the temperature implementing reacting field is by the mechanical milling method that is housed in the friction of motion of raw material in this regulation container etc. and the mode that rises, the reacting field temperature in this regulation container is than the hull-skin temperature height about 20 DEG C of this regulation container.In addition, the present inventor finds, when the mode by heating from the outside of regulation container implements mechanical milling method, the reacting field temperature in this regulation container is lower than the hull-skin temperature of this regulation container about 20 DEG C.Therefore, regardless of any mode, by controlling the hull-skin temperature of container, the reacting field temperature in container indirectly can be controlled.Can think like this, no matter be when heating from the outside of container, or when the outside not from container is heated, be about 20 DEG C due to the temperature difference inside and outside container can be made, therefore when using afore mentioned rules container, even if when cooling from the outside of container, the temperature difference inside and outside container is also about 20 DEG C, the hull-skin temperature height about 20 DEG C of the reacting field temperature container in the container when cooling from the outside of container.Therefore, even if when through quenching process synthesizing sulfide glass, by controlling the hull-skin temperature of container, the reacting field temperature in container also indirectly can be controlled.
Recycling engineering (hereinafter sometimes referred to as " S3 ") takes out from container and reclaims the operation of the chalcogenide glass synthesized S2.
Dry engineering (hereinafter sometimes referred to as " S4 ") is the chalcogenide glass reclaimed in S3 by drying, makes the operation evaporated simultaneously dropping into container with electrolyte raw material.Such as when S2 is the operation by the mechanical milling method synthesizing sulfide glass of dry type, S4 is unwanted.
By through above-mentioned S1 to S4, sulfide solid electrolyte can be manufactured.In manufacture method of the present invention, the reacting field temperature in container when controlling synthesizing sulfide glass in the mode meeting above-mentioned formula (1), on one side synthesizing sulfide glass.By such operation, control temperature, synthesizing sulfide glass, can prevent the Li reduced by ionic conduction performance thus on one side 2s-P 2s 5-LiI electrolyte and the formation of the specific crystalline phase confirmed, therefore, manufacturing method according to the invention, can manufacture the sulfide solid electrolyte that ionic conduction performance is improved.
In the above description, refer to the execution mode of the reacting field temperature in container when controlling synthesizing sulfide glass in decrystallized operation about the mode meeting above-mentioned formula (1) with x and y.As mentioned above, the reacting field temperature in container when controlling synthesizing sulfide glass in decrystallized operation by the mode meeting above-mentioned formula (1) with x and y, can manufacture the sulfide solid electrolyte that ionic conduction performance is improved.At this, in order to improve the productivity ratio of the sulfide solid electrolyte that ionic conduction performance is improved, in the scope meeting above-mentioned formula (1), preferably improve the reacting field temperature in decrystallized operation as far as possible.Consider from this viewpoint, in manufacture method of the present invention, in decrystallized operation, preferably make the reacting field temperature in container be more than 40 DEG C.From the same viewpoint, preferably not only meet above-mentioned formula (1) with x and y, the reacting field temperature in the container when mode also meeting following formula (2) controls synthesizing sulfide glass in decrystallized operation.
Y >-2.00x+1.52 × 10 2formula (2)
And then, as described later, by meeting above-mentioned formula (1) and/or above-mentioned formula (2) with x and y, and the reacting field temperature in the container of the mode meeting following formula (3) when controlling synthesizing sulfide glass in decrystallized operation, be easy to manufacture the sulfide solid electrolyte that ionic conduction performance is improved.Therefore, in the present invention, the reacting field temperature y in container when particularly preferably controlling synthesizing sulfide glass in decrystallized operation in the mode meeting above-mentioned formula (1), above-mentioned formula (2) and following formula (3).
Y≤-1.70x+1.655 × 10 2formula (3)
In manufacture method of the present invention, by controlling in the mode improving reacting field temperature y in the scope meeting above-mentioned formula (1) as far as possible, the generated time of chalcogenide glass can be shortened, therefore can reduce the manufacturing cost of sulfide solid electrolyte.
Embodiment
Below embodiment is shown, illustrates the present invention further.
1. the manufacture of sulfide solid electrolyte
[embodiment 1]
As electrolyte raw material, use lithium sulfide (Li 2s, Japan Chemical Industry system, purity 99.9%.Identical below.), phosphorus pentasulfide (P 2s 5, Aldrich system, purity 99.9%.Identical below) and lithium iodide (LiI, Aldrich system, identical below.)。Li is become with mol ratio 2s:P 2s 5: the mode of LiI=63.75:21.25:15 weighs these electrolyte raw material.Electrolyte raw material through weighing is dropped into together with tridecane container (45ml, the ZrO of planetary ball mill 2system) in, then in container, drop into the ZrO of diameter 5mm 2ball, fully closed container.In order to measure the temperature in mechanical lapping, the outer surface of container attaches heat label (ミ Network ロ Application society system).
This container is installed to the planetary ball mill (she makes made by rattan) of the function possessed from outside heating container, with design temperature 160 DEG C, per minute 488 turns continue within 4 hours, carry out mechanical lapping, synthesized the chalcogenide glass (85 (0.75Li of embodiment 1 thus 2s0.25P 2s 5) 15LiI).Now, in mechanical lapping enforcement, the hull-skin temperature (the arrival temperature of heat label) of container is 160 DEG C.Known by preliminary experiment, when heating this container from outside in mechanical lapping, the hull-skin temperature of the reacting field temperature container in container is low 20 DEG C, and the reacting field temperature therefore in embodiment 1 is 140 DEG C.
After mechanical lapping terminates, reclaim 85 (0.75Li from container 2s0.25P 2s 5) 15LiI, at 80 DEG C, carry out vacuumize to remove tridecane, obtain the sulfide solid electrolyte (85 (0.75Li of embodiment 1 thus 2s0.25P 2s 5) 15LiI).
[embodiment 2]
Except make from the design temperature during heating container of outside be except 150 DEG C, synthesizing sulfide glass (85 (0.75Li under the same conditions as example 1 2s0.25P 2s 5) 15LiI).The temperature of heat label during synthesizing sulfide glass is 149 DEG C, and the reacting field temperature therefore in embodiment 2 is 129 DEG C.
[embodiment 3]
Except make from the design temperature during heating container of outside be except 145 DEG C, synthesizing sulfide glass (85 (0.75Li under the same conditions as example 1 2s0.25P 2s 5) 15LiI).The temperature of heat label during synthesizing sulfide glass is 143 DEG C, and the reacting field temperature therefore in embodiment 3 is 123 DEG C.
[embodiment 4]
Li is become with mol ratio except using 2s:P 2s 5: lithium sulfide, phosphorus pentasulfide and lithium iodide that the mode of LiI=60:20:20 weighs as beyond electrolyte raw material, synthesizing sulfide glass (80 (0.75Li at the same conditions as example 3 2s0.25P 2s 5) 20LiI).Reacting field temperature in embodiment 4 is 123 DEG C.
[embodiment 5]
Except make from the design temperature during heating container of outside be except 135 DEG C, synthesizing sulfide glass (80 (0.75Li under the condition identical with embodiment 4 2s0.25P 2s 5) 20LiI).The temperature of heat label during synthesizing sulfide glass is 132 DEG C, and the reacting field temperature therefore in embodiment 5 is 112 DEG C.
[embodiment 6]
Except make from the design temperature during heating container of outside be except 125 DEG C, synthesizing sulfide glass (80 (0.75Li under the condition identical with embodiment 4 2s0.25P 2s 5) 20LiI).The temperature of heat label during synthesizing sulfide glass is 122 DEG C, and the reacting field temperature therefore in embodiment 6 is 102 DEG C.
[embodiment 7]
Li is become with mol ratio except using 2s:P 2s 5: lithium sulfide, phosphorus pentasulfide and lithium iodide that the mode of LiI=56.25:18.75:25 weighs as beyond electrolyte raw material, synthesizing sulfide glass (75 (0.75Li at the same conditions as example 3 2s0.25P 2s 5) 25LiI).Reacting field temperature in embodiment 7 is 123 DEG C.
[embodiment 8]
As electrolyte raw material, use lithium sulfide, phosphorus pentasulfide and lithium iodide.Li is become with mol ratio 2s:P 2s 5: the mode of LiI=52.5:17.5:30 weighs these electrolyte raw material.Electrolyte raw material through weighing is dropped into together with heptane container (500ml, the ZrO of planetary ball mill (Off リ ッ チ ュ society P5) 2system) in, then in container, drop into the ZrO of diameter 5mm 2ball, fully closed container.In order to measure the temperature in mechanical lapping, the outer surface of container attaches heat label (ミ Network ロ Application society system).
This container is installed on planetary ball mill, continues to carry out mechanical lapping in 60 hours with 280 turns per minute, synthesized the chalcogenide glass (70 (0.75Li of embodiment 8 thus 2s0.25P 2s 5) 30LiI).Now, in mechanical lapping enforcement, the hull-skin temperature (the arrival temperature of heat label) of container is 88 DEG C.Known by preliminary experiment, in the mechanical lapping of this container using volume 500ml not from outside heating container, the hull-skin temperature of the reacting field temperature container in container is high 20 DEG C, and the reacting field temperature therefore in embodiment 8 is 108 DEG C.
After mechanical lapping terminates, reclaim 70 (0.75Li from container 2s0.25P 2s 5) 30LiI, at 100 DEG C, carry out drying to remove heptane, obtain the sulfide solid electrolyte (70 (0.75Li of embodiment 8 thus 2s0.25P 2s 5) 30LiI).
[comparative example 1]
Except make from the design temperature during heating container of outside be except 170 DEG C, synthesizing sulfide glass (85 (0.75Li under the same conditions as example 1 2s0.25P 2s 5) 15LiI).The temperature of heat label during synthesizing sulfide glass is 169 DEG C, and the reacting field temperature therefore in comparative example 1 is 149 DEG C.
[comparative example 2]
Except make from the design temperature during heating container of outside be except 160 DEG C, synthesizing sulfide glass (80 (0.75Li under the condition identical with embodiment 4 2s0.25P 2s 5) 20LiI).The temperature of heat label during synthesizing sulfide glass is 160 DEG C, and the reacting field temperature therefore in comparative example 2 is 140 DEG C.
[comparative example 3]
Except make from the design temperature during heating container of outside be except 155 DEG C, synthesizing sulfide glass (75 (0.75Li under the condition identical with embodiment 7 2s0.25P 2s 5) 25LiI).The temperature of heat label during synthesizing sulfide glass is 155 DEG C, and the reacting field temperature therefore in comparative example 3 is 135 DEG C.
[comparative example 4]
Except making revolution when carrying out mechanical lapping be except 300 turns per minute, synthesizing sulfide glass (70 (0.75Li under the condition identical with embodiment 8 2s0.25P 2s 5) 30LiI).The temperature of heat label during synthesizing sulfide glass is 139 DEG C, and the reacting field temperature therefore in comparative example 4 is 119 DEG C.
2. analyze
[X-ray diffraction]
For the respective sulfide solid electrolyte manufactured by embodiment 1 to embodiment 8 and comparative example 1 to comparative example 4, by X-ray diffraction method, investigate the Li reduced by ionic conduction performance 2s-P 2s 5-LiI electrolyte and the Li confirmed 3pS 4-LiI crystalline phase and Li 3pS 4the presence or absence of crystalline phase.Investigation result is shown in Fig. 2.The longitudinal axis of Fig. 2 is reacting field temperature [DEG C], and transverse axis is the LiI content [mol%] in electrolyte raw material.In fig. 2, "○" means and does not confirm Li 3pS 4-LiI crystalline phase and Li 3pS 4crystalline phase, "×" means confirms Li 3pS 4-LiI crystalline phase, Li 3pS 4crystalline phase.Straight line shown in Fig. 2 is y=-2.00x+1.79 × 10 2and y=-2.00x+1.52 × 10 2(wherein, x is the content [mol%] of the LiI in electrolyte raw material, and y is reacting field temperature [DEG C]).Be explained, y=-2.00x+1.52 × 10 2be the straight line of-2.00 by the slope of the result of embodiment 5.
In addition, Fig. 3 and Fig. 4 is shown in the sulfide solid electrolyte of the condition manufacture of embodiment 1 with the X ray diffracting spectrum of the sulfide solid electrolyte of the condition manufacture of comparative example 1 and with the sulfide solid electrolyte of the condition of embodiment 8 synthesis with the X ray diffracting spectrum of the sulfide solid electrolyte of the condition of comparative example 4 synthesis.In figure 3, " ▼ " represents from Li 3pS 4the peak of-LiI crystalline phase, " ▽ " represents from Li 3pS 4the peak of crystalline phase.In addition, in the diagram, "○" represents the peak from LiI, and " ▼ " represents from Li 3pS 4the peak of-LiI crystalline phase.
[determination of ionic conductance]
By the respective sulfide solid electrolyte granulation manufactured with the condition of embodiment 8 and comparative example 4, calculate Li ionic conductance (normal temperature) from the resistance value adopting AC impedence method to measure.Be explained, in mensuration, use ソ ー ラ ト ロ Application 1260, condition determination is set to and applies voltage 5mV, measure frequency range 0.01MHz ~ 1MHz, read the resistance value of 100kHz, by thickness correction, be converted into Li ionic conductance.
3. result
The straight line of the result of the connection comparative example 1 shown in Fig. 2 and the result of comparative example 4 is y=-2.00x+1.79 × 10 2.Illustrated in the X ray diffracting spectrum of the X ray diffracting spectrum of comparative example 1 as shown in Figure 3 and the comparative example 4 shown in Fig. 4, to confirm Li the sulfide solid electrolyte of the condition manufacture of comparative example 1 to comparative example 4 3pS 4-LiI crystalline phase or Li 3pS 4-LiI crystalline phase and Li 3pS 4crystalline phase.And, (100-x) (0.75Li of comparative example 1 to comparative example 4 2s0.25P 2s 5) between x in xLiI and reacting field temperature y, y>=-2.00x+1.79 × 10 2relation set up.On the other hand, illustrated in the X ray diffracting spectrum of the X ray diffracting spectrum of embodiment 1 as shown in Figure 3 and the embodiment 8 shown in Fig. 4, are unbodied (amorphous) with the sulfide solid electrolyte of the condition manufacture of embodiment 1 to embodiment 8, from these electrolyte, do not confirm Li 3pS 4-LiI crystalline phase and Li 3pS 4crystalline phase.And embodiment 1 to embodiment 8 meets y <-2.00x+1.79 × 10 2.In addition, because the straight line of the result by embodiment 1 and embodiment 7 is y=-1.70x+1.655 × 10 2, therefore embodiment 1 to embodiment 8 meets y≤-1.70x+1.655 × 10 2.In addition, embodiment 1 to embodiment 4, embodiment 7 and embodiment 8 also meet y >-2.00x+1.52 × 10 2.
In addition, with the Li ionic conductance of the sulfide solid electrolyte of the condition manufacture of embodiment 8 for 1.76 × 10 -3s/cm, on the other hand, with the Li ionic conductance of the sulfide solid electrolyte of the condition manufacture of comparative example 4 for 1.50 × 10 -3s/cm.That is, Li is not confirmed 3pS 4-LiI crystalline phase and Li 3pS 4the Li ionic conductance of the sulfide solid electrolyte of crystalline phase is higher than confirming Li 3pS 4-LiI crystalline phase, Li 3pS 4the Li ionic conductance of the sulfide solid electrolyte of crystalline phase.
According to more than, confirm by through to meet y <-2.00x+1.79 × 10 2mode control reacting field temperature, the process of synthesizing sulfide glass manufactures sulfide solid electrolyte, can manufacture the Li that ionic conduction performance is improved 2s-P 2s 5-LiI electrolyte.In addition we know, by passing through to meet y≤-1.70x+1.655 × 10 2mode control reacting field temperature, the process of synthesizing sulfide glass manufactures sulfide solid electrolyte, easily manufactures the Li that ionic conduction performance is improved 2s-P 2s 5-LiI electrolyte.
As described above, in embodiment 1 to embodiment 8, when the mechanical milling method synthesizing sulfide glass by wet type, by controlling reacting field temperature, the Li that ionic conduction performance is improved can be manufactured 2s-P 2s 5-LiI electrolyte.At this, mechanical milling method is by making the raw material of solid react the gimmick of synthesizing target substance each other, therefore can think that technological thought of the present invention can be applicable to synthesize Li by making the raw material of solid react each other 2s-P 2s 5during-LiI electrolyte.And can think, at manufacture Li 2s-P 2s 5during-LiI electrolyte, even if when using the method beyond mechanical milling method, be synthesize Li by making the raw material of solid react each other in the method 2s-P 2s 5when the electrolytical method of-LiI, by controlling reacting field temperature during this synthesis, also can manufacture the Li that ionic conduction performance is improved 2s-P 2s 5-LiI electrolyte.

Claims (6)

1. the manufacture method of sulfide solid electrolyte, it comprises:
Drop into operation: will for the manufacture of with general formula (100-x) (0.75Li 2s0.25P 2s 5) xLiI be the sulfide solid electrolyte of main body raw material drop into container, wherein, x is 0 < x < 100, and
Decrystallized operation: by decrystallized for described raw material after described input operation,
The mode meeting following formula (1) with the reacting field temperature y [DEG C] in the described container in the x contained in described general formula and described decrystallized operation controls the reacting field temperature in described container,
Y <-2.00x+1.79 × 10 2formula (1).
2. the manufacture method of sulfide solid electrolyte according to claim 1, described x is >=20.
3. the manufacture method of the sulfide solid electrolyte described in claim 1 or 2, in described decrystallized operation, makes the reacting field temperature in described container be more than 40 DEG C.
4. the manufacture method of the sulfide solid electrolyte described in claim 1 or 2, further, the mode meeting following formula (2) with described x and described reacting field temperature y controls the reacting field temperature in described container,
Y >-2.00x+1.52 × 10 2formula (2).
5. the manufacture method of the sulfide solid electrolyte described in any one of Claims 1 to 4, in described decrystallized operation, gives heat energy in described container.
6. the manufacture method of the sulfide solid electrolyte described in any one of Claims 1 to 5, described decrystallized operation is utilize the mechanical milling method of wet type by decrystallized for described raw material operation.
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